KR102375769B1 - aqueous polymer composition - Google Patents

Abstract

The present invention provides aqueous polymer compositions and aqueous coating compositions comprising such aqueous polymer compositions that exhibit balanced antifouling properties, freeze-thaw stability, and anti-clogging properties.

Description

aqueous polymer composition

The present invention relates to aqueous polymer compositions, and aqueous coating compositions comprising the same, having zero or low volatility organic compounds (VOCs).

Aqueous or waterborne coating compositions are becoming more and more important than solvent-based coating compositions in order to create less environmental problems. The coatings industry has always been interested in developing coating compositions that have no VOC, or substantially reduced or low VOC, for example, a VOC of 5 grams per liter (g) or less of the coating composition. However, aqueous coating compositions, particularly low VOC coating compositions, have typically suffered from a lack of freeze-thaw (F/T) stability during transport and storage.

Recently developed cryoprotectants that do not contribute to VOC, such as polyethylene glycol (PEG) and tristyrylphenol ethoxylate, can be used to improve the F/T stability of the coating composition. For example, European Patent No. 2,703,434 describes the use of alkoxylated tristyrylphenol or alkoxylated tributylphenol to improve the freeze-thaw stability of latex dispersions and paint formulations. Unfortunately, the addition of these compounds impairs the stain resistance of the resulting coating. Some advanced applications require a coating having a total decontamination score of at least 60, as measured by the GB/T9780-2013 method. The use of phosphate surfactants has the advantage of improving the antifouling properties of the coating. However, an increase in brush clogging was observed when a phosphate surfactant was used in the coating composition. Moreover, other surfactants, such as non-ionic surfactants, are useful for reducing brush clogging, but usually weaken the antifouling performance.

Accordingly, there remains a need to develop aqueous polymer compositions particularly suitable for zero or low VOC coating applications in order to balance coating performance properties including antifouling properties, freeze-thaw stability and anti-clogging properties.

The present invention provides an aqueous polymer composition by combining a polymer comprising structural units of an allyl alkoxylated phosphorus-containing monomer, a functional silane and a phosphorus-containing surfactant. Aqueous polymer compositions can provide an improved balance of antifouling properties, freeze-thaw stability and anti-clogging properties to coating compositions comprising them.

In a first aspect, the present invention is an aqueous polymer composition comprising:

(i) from 0.1% to 10% by weight, based on the weight of the polymer, of a polymer comprising structural units of an allyl alkoxylated phosphorus-containing monomer having the structure of formula (I);

(I),

(I);

wherein m is 2 to 5, n is 0 to 10, 1 is 1 or 2, Y is -OH or -O ^- M ⁺ , wherein M is a metal ion or an ammonium ion;

(ii) a functional silane selected from an epoxy functional polysiloxane oligomer, an epoxy functional silane compound, an ethylenically unsaturated compound having at least one alkoxysilane functional group, or mixtures thereof; and

(iii) a phosphorus-containing surfactant having the structure of formula (V);

(V),

(V),

wherein R is C ₈ -C ₃₀ alkyl, AO is an alkoxylated group, b is 1 to 2, a is 1 to 30, and N ⁺ is a metal ion or ammonium ion.

In a second aspect, the present invention has a VOC content of 5 g/L or less, wherein the aqueous polymer composition of the first aspect and at least one selected from the group consisting of dispersants, fusing agents, wetting agents, thickeners, defoamers, pigments and extenders An aqueous coating composition comprising urea.

As used herein, “Acrylic” refers to (meth)acrylic acid, (meth)alkyl acrylate, (meth)acrylamide, (meth)acrylonitrile and variants thereof, such as (meth)hydroxyalkyl acrylate. include Throughout this specification, the word fragment "(meth)acryl" refers to both "methacryl" and "acryl". For example, (meth)acrylic acid refers to both methacrylic acid and acrylic acid, and methyl (meth)acrylate refers to both methyl methacrylate and methyl acrylate.

"Glass transition temperature" or "T _g " in the present invention can be determined by a variety of techniques including, for example, differential scanning calorimetry ("DSC"), or the Fox equation ) can be measured by the lower limit calculation. The specific values of T _g reported herein were calculated using the Fox equation (TG Fox, Bull. Am. Physics Soc., Volume 1, Issue No. 3, page 123 (1956)). For example, for the calculation of the T _g of the copolymer of monomers M ₁ and M ₂ ,

,

,

where T _g (calc.) is the calculated glass transition temperature for the copolymer, w(M ₁ ) is the weight fraction of monomer M ₁ in the copolymer, and w(M ₂ ) is the monomer M ₂ in the copolymer is the weight fraction of , T _g (M ₁ ) is the glass transition temperature of the homopolymer of monomer M ₁ , T _g (M ₂ ) is the glass transition temperature of the homopolymer of monomer M ₂ ; All temperatures are K. Glass transition temperatures of homopolymers can be found, for example, in "Polymer Handbook", edited by J. Brandrup and EH Immergut, Interscience Publishers.

The term structural unit (also known as polymerized unit) described herein of a named monomer refers to the remainder of the monomer after polymerization, or the monomer in its polymerized form. For example, the structural unit of methyl methacrylate is shown as follows:

,

,

Here, the dotted line indicates the point of attachment of the structural unit to the polymer backbone.

As used herein, “aqueous” compositions and dispersions refer to particles dispersed in an aqueous medium. "Aqueous medium" as used herein means water and 0 to 30% by weight, based on the weight of the medium, of water-miscible compound(s) such as alcohols, glycols, glycol ethers, glycol esters, and the like .

The aqueous polymer composition of the present invention comprises a polymer. The polymer is obtained by free-radical polymerization, preferably emulsion polymerization (thus forming an emulsion polymer), of a mixture of at least one allyl alkoxylated phosphorus-containing monomer and a monomer comprising one or more monomers described herein. The polymer comprises structural units of one or more allyl alkoxylated phosphorus-containing monomers. The allyl alkoxylated phosphorus-containing monomer may have the structure of formula (I):

(I),

(I);

wherein, in formula (I), m is 2 to 5, preferably 3 to 5; n is 0 to 10, preferably 0 to 5; l is 1 to 2, preferably 2; Y is -OH or -O ^- M ⁺ , where M may be a metal ion or an ammonium ion. Preferably, m is 3 to 5, n is 0 to 5, Y is -O ^- M ⁺ , where M may be a metal ion or an ammonium ion.

Preferably, the allyl alkoxylated phosphorus-containing monomer is

의 구조를 갖는 단량체, 및/또는 이의 염, 바람직하게는 암모늄 염을 포함한다.

a monomer having the structure of, and/or a salt thereof, preferably an ammonium salt.

Suitable commercially available allyl alkoxylated phosphorus-containing monomers include ADEKA REASOAP PP-70 (allyl alkyloxylated phosphorus ester monomer having three propylene oxide chains) available from Adeka Company, a salt thereof, or mixtures thereof. include

Compositions useful in the present invention comprise at least 0.1 wt%, at least 0.3 wt%, at least 0.5 wt%, at least 1.0 wt%, or even at least 2 wt%, and at the same time up to 10 wt%, 8 wt%, based on the weight of the polymer. % or less, 7 wt% or less, 6 wt% or less, 5 wt% or less, or even 3 wt% or less of structural units of the allyl alkoxylated phosphorus-containing monomer. As used herein, "weight of the polymer" refers to the dry or solid weight of the polymer.

The polymers useful in the present invention may also include structural units of one or more stabilizing monomers. The stabilizing monomer may be an ethylenically unsaturated monomer having at least one functional group selected from carboxyl, carboxylic acid anhydride, sulfonic acid, amide, sulfonate, phosphonate, or combinations thereof. Examples of suitable stabilizing monomers include acid-containing monomers such as α,β-ethylenically unsaturated carboxylic acids including methacrylic acid (MAA), acrylic acid (AA), itaconic acid (IA), maleic acid, or fumaric acid; or a monomer (eg, anhydride, (meth)acrylic anhydride, or maleic anhydride) having an acid-forming group that generates or is subsequently converted to such an acid group; Ammonium salt of sodium styrene sulfonate (SSS), sodium vinyl sulfonate (SVS), 2-acrylamido-2-methylpropanesulfonic acid (AMPS), 2-acrylamido-2-methyl-1-propane sulfonic acid; sodium salt of allyl ether sulfonate and the like; Acrylamide, methacrylamide, mono-substituted (meth)acrylamide, N-methylacrylamide, N-ethylacrylamide, N-isopropylacrylamide, N-butylacrylamide, N-tertiary butylacrylamide, N -2-ethylhexyl acrylamide, N,N-dimethylacrylamide, N,N-diethylacrylamide; or mixtures thereof. Preferred stabilizing monomers include α, β-ethylenically unsaturated carboxylic acids such as methacrylic acid, acrylic acid, or mixtures thereof. The polymer comprises, based on the weight of the polymer, at least 0, at least 0.5 wt%, at least 1 wt%, or even at least 1.5 wt%, and at the same time no more than 5 wt%, no more than 3 wt%, or even no more than 2.5 wt% of stabilizing monomers may contain structural units of

The polymers useful in the present invention may further comprise structural units of one or more ethylenically unsaturated alkoxylated (meth)acrylate monomers. The ethylenically unsaturated alkoxylated (meth)acrylate monomer may have the structure of formula (II):

(II),

(II);

wherein R ₁ is a hydrogen atom or a methyl group, X is a divalent organic polyalkylene oxide group comprising 1 to 50 alkylene oxide units, and R ₂ is a hydrogen atom or an aliphatic having 1 to 20 carbon atoms. or an aromatic hydrocarbon group. In one embodiment, X is a polyalkylene oxide group, preferably comprising ethylene oxide (EO) units, propylene oxide (PO) units, or a combination of ethylene oxide and propylene oxide units. The ethylene oxide units and propylene oxide units may, for example, be positioned alternately or may be present in the form of polyethylene oxide and/or polypropylene oxide blocks. A polyalkylene oxide group can include one or more, two or more, three or more, or even four or more, and at the same time no more than 50, no more than 40, no more than 30, or even no more than 20 alkylene oxide units. The radical R ₂ is preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms; Preferably, R ₂ is a C ₁ -C ₈ alkyl group, a C ₁ -C ₄ alkyl group, or a hydrogen atom. Suitable commercially available ethylenically unsaturated alkoxylated (meth)acrylate monomers include VISIOMER MPEG-1005MA (methoxy polyethylene glycol 1000 methacrylate) available from Evonik Company. The polymer is at least 0, at least 0.1 wt%, at least 0.5 wt%, at least 0.8 wt%, at least 1 wt%, at least 1.5 wt%, or even at least 3 wt%, and at the same time no more than 5 wt%, based on the weight of the polymer. , 4 wt% or less, 3 wt% or less, 2.5 wt% or less, or even 2 wt% or less of structural units of an ethylenically unsaturated alkoxylated (meth)acrylate monomer.

Polymers useful in the present invention also include one or more ethylenically unsaturated monomers having at least one functional group different from the stabilizing monomer (hereinafter "functional-group-containing ethylenically unsaturated monomer"). may contain structural units of The functional group may be selected from carbonyl, acetoacetoxy, acetoacetamide, ureido, imide, amino, hydroxyl, alkoxysilane, or phosphorus groups. When the functional group is an alkoxysilane group, the functional-group-containing ethylenically unsaturated monomer includes an ethylenically unsaturated compound having at least one alkoxysilane functional group as described in the Functional Silanes section below. Examples of suitable functional-group-containing ethylenically unsaturated monomers include vinyltrialkoxysilanes such as vinyltrimethoxysilane or (meth)acryloxyalkyltrialkoxysilane; acetoacetoxyethyl methacrylate (AAEM); vinyl phosphonic acid, allyl phosphonic acid, phosphoalkyl (meth)acrylates such as phosphoethyl (meth)acrylate, phosphopropyl (meth)acrylate, phosphobutyl (meth)acrylate, or salts thereof; diacetone acrylamide (DAAM), methylacrylamidoethyl ethylene urea, hydroxy-functional (meth)acrylic acid alkyl esters such as hydroxyethyl methacrylate and hydroxypropyl methacrylate, or mixtures thereof. . Preferred functional-group-containing ethylenically unsaturated monomers are selected from acetoacetoxyethyl methacrylate, diacetone acrylamide or mixtures thereof. The polymer is at least 0, at least 0.1 wt%, at least 0.5 wt%, at least 1 wt%, at least 1.5 wt%, at least 2 wt%, at least 2.5 wt%, or even at least 3 wt%, based on the weight of the polymer, and at the same time 10 wt% or less, 8 wt% or less, or even 5 wt% or less of functional-group-containing ethylenically unsaturated monomer structural units.

The polymers useful in the present invention may also include structural units of one or more additional ethylenically unsaturated nonionic monomers that differ from the monomers described above. As used herein, the term “nonionic monomer” refers to a monomer that does not have an ionic charge at pH = 1-14. Suitable ethylenically unsaturated nonionic monomers include, for example, monoethylenically unsaturated nonionic monomers, which are alkyl esters of (methyl) acrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, lauryl acrylate, methyl methacrylate, butyl methacrylate, isodecyl methacrylate, lauryl methacrylate, (meth)acrylonitrile, or mixtures thereof. . Preferably, the additional ethylenically unsaturated nonionic monomer is selected from the group consisting of methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and styrene. The polymer may comprise from 75% to 99.3% by weight, from 80% to 95% by weight, or from 87% to 94% by weight of additional ethylenically unsaturated nonionic monomer structural units, based on the weight of the polymer.

In some embodiments, the polymer comprises, by weight of the polymer:

0.1% to 5% by weight of structural units of an allyl alkoxylated phosphorus-containing monomer,

0.5% to 3% by weight of structural units of stabilizing monomers,

0.1% to 5% by weight of structural units of an ethylenically unsaturated alkoxylated (meth)acrylate monomer, and

87 wt % to 99.3 wt % additional comprising, for example, an alkyl ester of (methyl) acrylic acid, such as methyl methacrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, or mixtures thereof Structural unit of an ethylenically unsaturated nonionic monomer.

The types and levels of the above-described monomers for preparing the polymer are -10 °C or higher, 0 °C or higher, 10 °C or higher, 20 °C or higher, or even 30 °C or higher, and simultaneously 70 °C or lower, 60 °C or lower, 50 °C or lower. , or even a polymer having a glass transition temperature (Tg) of 40° C. or less. The Tg of a polymer can be calculated herein using the Fox equation described above.

The aqueous polymer composition of the present invention may further comprise at least one functional silane selected from an epoxy functional polysiloxane oligomer, an epoxy functional silane compound, an ethylenically unsaturated compound comprising at least one alkoxysilane functionality, or mixtures thereof. can In some embodiments, the aqueous polymer composition of the present invention comprises an epoxy functional polysiloxane oligomer.

The aqueous polymer composition of the present invention may comprise one or more epoxy functional polysiloxane oligomers, typically saturated epoxy functional polysiloxane oligomers. As used herein, “oligomer” refers to a polymer having a number-average molecular weight of 200 to 3,000, 300 to 2,000, or 350 to 1,000. The number-average molecular weight (Mn) of the epoxy functional polysiloxane oligomer can be determined by gel permeation chromatography (GPC) using an Agilent 1200. Samples were dissolved in tetrahydrofuran (THF) to a concentration of 5 mg/mL and then filtered through a 0.45 μm polytetrafluoroethylene (PTFE) filter prior to GPC analysis. The conditions of the GPC analysis were as follows, columns: one PLgel GUARD column (10 μm, 50 x 7.5 mm), two Polymer Laboratories Mixed E columns (7.8 x 300 mm) side by side; column temperature: 40°C; mobile phase: THF; flow rate: 1.0 mL/min; Injection volume: 50 L; Detector: Agilent refractive index detector, 40°C; and Calculation curves: PL polystyrene narrow standards with molecular weights between 580 and 19,760 g/mol (using Polynom 3 Fitness). The peak molecular weight (Mp) used for the narrow assay is the value converted from the Mp of each PS standard using the formula: M _p = 1.0951 Mp of PS ^0.9369 .

Epoxy functional polysiloxane oligomers useful in the present invention may have the structure of formula (III):

(III),

(III),

where x is 0 to 14; preferably 0 to 4, 1 to 4, or 1 to 3; R ₃ is —CH ₂ CH ₂ CH ₂ —.

The epoxy functional polysiloxane oligomer may be a mixture of oligomers having the structure of formula (III) with different x values, for example 0, 1, 2 or 3. In one embodiment, the epoxy-containing polysiloxane oligomer useful in the present invention comprises (i) a polysiloxane of formula (III), wherein p = 0; (ii) a polysiloxane of formula (III), wherein p = 1; (iii) a polysiloxane of formula (III), wherein p = 2; and (iv) a polysiloxane of formula (III), wherein p=3. Suitable commercially available epoxy functional polysiloxane oligomers are available from Momentive Performance Material Inc. CoatOSil MP 200 polysiloxane oligomer available from the Company.

The aqueous polymer composition of the present invention may comprise one or more epoxy functional silane compounds different from the epoxy functional polysiloxane oligomer. The epoxy functional silane compound is typically a saturated alkoxylated silane having an epoxy group. The epoxy functional silane compound may have at least one hydrolyzable silane group. Preferred epoxy functional silane compounds have the general formula (IV):

(IV),

(IV),

wherein R ³ represents an alkyl group having 1 to 6 carbon atoms; OR ³ group represents an alkoxy group, including, for example, a methoxy, ethoxy or acetoxy group, or a combination thereof; R ⁴ represents a divalent organic group having a molecular weight of 200 or less, preferably R ⁴ is a C ₁ -C ₁₀ , C ₁ -C ₅ , or C ₁ -C ₃ alkylene group; R ⁵ represents a hydrogen atom or an alkyl, aryl, or aralkyl group having 1 to 20 carbon atoms; q is 1, 2 or 3. Examples of suitable epoxy functional silane compounds include 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl methyldiethoxysilane, 3-glycidyloxypropyl diloxypropyl methyldimethoxysilane, or mixtures thereof. Suitable commercially available epoxy functional silane compounds are available from Momentive Performance Material Inc. Silquest A-187 gamma-glycidoxypropyltrimethoxysilane from the Company.

The aqueous polymer composition of the present invention comprises at least one ethylenically unsaturated compound having at least one alkoxysilane functional group different from the epoxy functional silane compound (hereinafter "unsaturated alkoxysilane functional compound"). can do. The unsaturated alkoxysilane functional compound preferably has a hydrolyzable alkoxysilane functional group. Suitable unsaturated alkoxysilane functional compounds are, for example, vinyltrialkoxysilanes such as vinyltrimethoxysilane; alkylvinyldialkoxysilane; (meth)acryloxyalkyltrialkoxysilanes such as (meth)acryloxyethyltrimethoxysilane and (meth)acryloxypropyltrimethoxysilane; derivatives thereof, and combinations thereof.

The functional silane useful in the present invention (i.e., an epoxy functional polysiloxane oligomer, an epoxy functional silane compound, and/or an unsaturated alkoxysilane functional compound) comprises at least 0.05 wt%, at least 0.1 wt%, based on the weight of the polymer; 0.15 wt% or more, 0.2 wt% or more, 0.25 wt% or more, 0.3 wt% or more, 0.4 wt% or more, or even 0.5 wt% or more, and at the same time 3 wt% or less, 2.5 wt% or less, 2 wt% or less, 1.5 wt% or more % by weight or less, or even up to 1% by weight combined.

The aqueous polymer composition of the present invention also comprises at least one phosphorus-containing surfactant having the structure of formula (V),

(V),

(V),

wherein R is C ₈ -C ₃₀ alkyl, AO is an alkoxylated group (ie, alkylene oxide), b is 1-2, a is 1-30, and N ⁺ is a metal ion or ammonium ion can R may be C ₈ -C ₁₈ alkyl, preferably C ₁₀ -C ₁₅ alkyl, more preferably C ₁₁ -C ₁₃ alkyl. AO may be an ethoxylated group (ie, an ethylene oxide group), a propoxylated group (ie, a propylene oxide group), or a combination thereof, preferably an ethoxylated group. Preferably, the value of formula (V) is from 1 to 30, from 3 to 15, or from 5 to 10. Preferably, b is 2. Suitable commercially available phosphorus-containing surfactants may include, for example, RHODAFAC RS610 alkyl ethoxylated phosphorus-containing surfactants having 6 ethylene oxide units available from Solvay Compan. The phosphorus-containing surfactant may be added to the mixture of monomers used to prepare the polymer during, after, or combinations thereof during polymerization. The aqueous polymer composition of the present invention comprises at least 0.1 wt%, at least 0.3 wt%, at least 0.5 wt%, at least 1 wt%, at least 2 wt%, at least 2.5 wt%, or even 3 wt%, based on the weight of the polymer. or more, and at the same time up to 5 wt%, up to 4.5 wt%, up to 4 wt%, or even up to 3.5 wt% of a phosphorus-containing surfactant. The weight ratio of phosphorus-containing surfactant to allyl alkoxylated phosphorus-containing monomer used to prepare the polymer is 5:95 to 95:5, 10:90 to 90:10, 30:70 to 70:30, 40:60 to 50:50, preferably from 5:95 to 50:50.

The aqueous polymer composition of the present invention is prepared by first forming, by free-radical polymerization, preferably emulsion polymerization, a polymer of a mixture of a monomer comprising an allyl alkoxylated phosphorus-containing monomer with one or more of the monomers described above. The total weight concentration of the mixture of monomers described above to prepare the polymer is equivalent to 100%. The mixture of monomers is added neat or as an emulsion in water; or during the reaction period to prepare the polymer, in one or more additions or continuously, linearly or out of sequence. Suitable temperatures for the free-radical polymerization process may be less than 100°C, in the range of 30°C to 95°C, or in the range of 50°C to 90°C. One or more surfactants may be used to prepare the polymer. The surfactant may include a phosphorus-containing surfactant described above, an additional surfactant different from the phosphorus-containing surfactant, or a combination thereof. The phosphorus-containing surfactant and/or additional surfactant may be added before, during or after polymerization of the monomer mixture, or at the time of a combination thereof. These additional surfactants may include anionic and/or nonionic emulsifiers. Examples of suitable additional surfactants include DISPONIL FES 32 fatty alcohol ether sulfate available from BASF, TERGITOL™ 15-S-40 secondary alcohol ethoxylate available from The Dow Chemical Company (TERGITOL is a trade name of The Dow Chemical Company) ) is included. The additional surfactant used is usually from 0 to 5% by weight, from 0.5% to 3% by weight, or from 0.8% to 2% by weight, based on the total weight of the monomers used to prepare the polymer. The functional silane may be added after polymerization of the monomer mixture.

In the polymerization process, free radical initiators and/or chain transfer agents may be used. The polymerization process may be thermally initiated or redox initiated emulsion polymerization. Examples of suitable free radical initiators include hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, ammonium and/or alkali metal persulfates, sodium perborate, superphosphate, and salts thereof; potassium permanganate, and ammonium or alkali metal salts of peroxydisulfuric acid. Free radical initiators can usually be used at a level of 0.01% to 3.0% by weight, based on the total weight of the monomers. A redox system comprising the initiator described above coupled with a suitable reducing agent may be used in the polymerization process. Examples of suitable reducing agents are sodium sulfoxylate formaldehyde, ascorbic acid, isoascorbic acid, alkali metal and ammonium salts of sulfur-containing acids such as sodium sulfite, bisulfite, thiosulfate, hydrosulfite, sulfide, hydrosulfide or dithionite, formalinsulfinic acid, acetone bisulfite, glycolic acid, hydroxymethanesulfonic acid, glyoxylic acid hydrate, lactic acid, glyceric acid, malic acid, tartaric acid and salts of the preceding acids. Metal salts of iron, copper, manganese, silver, platinum, vanadium, nickel, chromium, palladium, or cobalt may be used to catalyze the redox reaction. A chelating agent for metals may optionally be used. Examples of suitable chain transfer agents include 3-mercaptopropionic acid, n-dodecyl mercaptan, methyl 3-mercaptopropionate, butyl 3-mercaptopropionate, benzenethiol, azelaic alkyl mercaptan, or their including mixtures. The chain transfer agent is an effective amount for controlling the molecular weight of the polymer, for example, from 0 to 1 wt%, 0.1 wt% to 0.5 wt%, or 0.15 wt% to based on the total weight of the monomers used in the preparation of the polymer. 0.4% by weight may be used.

After completion of the polymerization, the resulting polymer dispersion can be neutralized with one or more bases as neutralizing agent, for example to a pH value of at least 6, 6 to 10, or 7 to 9. The base can induce partial or complete neutralization of the ionic or potentially ionic groups of the polymer. Examples of suitable bases include ammonia; alkali metal or alkaline earth metal compounds such as sodium hydroxide, potassium hydroxide, calcium hydroxide, zinc hydroxide, magnesium hydroxide, sodium carbonate; primary, secondary and tertiary amines such as triethyl amine, ethylamine, propylamine, monoisopropylamine, monobutylamine, hexylamine, ethanolamine, diethyl amine, dimethyl amine, tributylamine, triethanolamine, Dimethoxyethylamine, 2-ethoxyethylamine, 3-ethoxypropylamine, dimethylethanolamine, diisopropanolamine, morpholine, ethylenediamine, 2-diethylaminoethylamine, 2,3-diaminopropane, 1 ,2-propylenediamine, neopentanediamine, dimethylaminopropylamine, hexamethylenediamine, 4,9-dioxadodecane-1,12-diamine, polyethyleneimine or polyvinylamine; aluminum hydroxide; or mixtures thereof.

Polymers useful in the present invention have an average particle size of 50 nanometers (nm) to 500 nm, 80 nm to 200 nm, or 90 nm to 150 nm as measured by a Brookhaven BI-90 or 90 Plus particle sizer. can have

When antifouling, F/T stability and anti-clogging properties are desired, the aqueous polymer compositions of the present invention are particularly useful for zero or low VOC coating applications. The aqueous coating composition of the present invention comprising the aqueous polymer composition has a zero or low VOC, i.e., a volatile organic compound (VOC) of no more than 5 grams per liter (g/L) of the aqueous coating composition as per GB18582-2008 method. have Preferably, the VOC content of the aqueous coating composition is less than 5 g/L, less than 3 g/L, less than 2.5 g/L, less than 2 g/L, less than 1 g/L. Surprisingly, the aqueous coating composition of the present invention can also provide the coating film with improved antifouling properties, surprisingly indicated by a total stain removal score of at least 60 when by the GB/T 9780-2013 method, whereas The aqueous coating composition also has good freeze-thaw stability and good anti-clogging properties by the test methods described in the Examples section below. "Good freeze-thaw stability" (i.e., freeze-thaw stability) indicates that the composition is subjected to three freeze-thaw cycles (-6°C to room temperature) according to the test method described in the Examples section below. This means that no coagulation and/or aggregation is exhibited. GB 18582-2008 method herein is a national standard for upholstery and recycled material-restriction of hazardous substances in interior building coatings, which was published on April 1, 2008 and was implemented on October 1, 2008. GB/T 9780-2013 method herein is a national standard for a test method for dust pickup resistance and decontamination of films and paints of architectural coatings, published on November 27, 2013 and August 2014 was conducted on day 1. GB/T9780-2013 and GB 18582-2008 methods were both published by China's General Administration of Quality Supervision, Inspection and Quarantine, and China's Standardization Administration.

The aqueous coating composition of the present invention may also include one or more pigments and/or extenders. As used herein, the term “pigment” refers to a particulate inorganic material that can substantially contribute to the opacity or hiding ability of a coating. Such materials typically have a refractive index greater than 1.8 and include inorganic and organic pigments. Examples of suitable inorganic pigments include titanium dioxide (TiO ₂ ), zinc oxide, zinc sulfide, iron oxide, barium sulfate, barium carbonate, or mixtures thereof. A preferred pigment used in the present invention is TiO ₂ . TiO ₂ may also be available in concentrated dispersion form. The term “extender” refers to a particulate inorganic material having a refractive index of 1.8 or less and greater than 1.3. Examples of suitable extenders include calcium carbonate, aluminum oxide (Al ₂ O ₃ ), clay, calcium sulfate, aluminosilicates, silicates, zeolites, mica, diatomaceous earth, solid or hollow glass, ceramic beads, and opaque polymers such as The Dow ROPAQUE™ Ultra E available from Chemical Company (ROPAQUE is a trade name of The Dow Chemical Company), or mixtures thereof. The aqueous coating composition may have a pigment volume concentration (PVC) of 30% to 70%, 40% to 60%, or 45% to 55%. The PVC of the coating composition can be determined according to the following formula:

The aqueous coating composition of the present invention may further comprise one or more anti-foaming agents. As used herein, "Defoamer" refers to a chemical additive that reduces and interferes with the formation of foam. The anti-foaming agent may be a silicone-based anti-foaming agent, a mineral oil-based anti-foaming agent, an ethylene oxide/propylene oxide-based anti-foaming agent, or mixtures thereof. Suitable commercially available antifoam agents include, for example, TEGO Airex 902 W and TEGO Foamex 1488 polyether siloxane copolymer emulsions, both available from TEGO, BYK-024 silicone antifoam available from BYK, or mixtures thereof. includes The antifoam agent may be present generally in an amount of 0 to 0.5% by weight, 0.05% to 0.4% by weight, or 0.1% to 0.3% by weight, based on the total weight of the aqueous coating composition.

The aqueous coating composition of the present invention may further comprise one or more thickening agents (also known as "rheology modifiers"). Thickeners may include polyvinyl alcohol (PVA), acid derivatives, acid copolymers, urethane related thickeners (UATs), polyether urea polyurethanes (PEUPU), polyether polyurethanes (PEPU), or mixtures thereof. Examples of suitable thickeners include alkali expandable emulsions (ASEs) such as sodium or ammonium neutralized acrylic acid polymers; hydrophobically modified alkali swellable emulsions (HASEs), such as hydrophobically modified acrylic acid copolymers; associative thickeners such as hydrophobically modified ethoxylated urethanes (HEUR); and cellulosic thickeners such as methyl cellulose ether, hydroxymethyl cellulose (HMC), hydroxyethyl cellulose (HEC), hydrophobically-modified hydroxy ethyl cellulose (HMHEC), sodium carboxymethyl cellulose (SCMC), sodium carboxymethyl 2 -hydroxyethyl cellulose, 2-hydroxypropyl methyl cellulose, 2-hydroxyethyl methyl cellulose, 2-hydroxybutyl methyl cellulose, 2-hydroxyethyl ethyl cellulose, and 2-hydroxypropyl cellulose . Preferably, the thickener is selected from HASE, HEC, HEUR, or mixtures thereof. The thickener may be present generally in an amount of 0 to 3.0% by weight, 0.1% to 1.5% by weight, or 0.2% to 1.2% by weight, based on the total weight of the aqueous coating composition.

The aqueous coating composition of the present invention may further comprise one or more wetting agents. As used herein, "wetting agent" refers to a chemical additive that reduces the surface tension of the coating composition, causing the coating composition to more readily diffuse or penetrate into the substrate surface. Wetting agents are polycarboxylates and may be anionic, zwitterionic, or non-ionic. Suitable commercially available wetting agents include, for example, TRITON ^™ CF-10 nonionic surfactant available from The Dow Chemical Company (TRITON is a trade name of the Dow Chemical Company), acetacetylene diol available from Air Products. based SURFYNOL 10 nonionic wetting agents, BYK-346 and BYK-349 polyether-modified siloxanes, both available from BYK, or mixtures thereof. The wetting agent may be present in an amount of 0 to 1.0 wt%, 0.1 wt% to 0.8 wt%, or 0.2 wt% to 0.6 wt%, based on the total weight of the aqueous coating composition.

The aqueous coating composition of the present invention may further comprise one or more fusing agents. "Coalescent" herein refers to a slow-evaporating solvent that fuses polymer particles into a continuous membrane under ambient conditions. Examples of suitable fusing agents include 2-n-butoxyethanol, dipropylene glycol n-butyl ether, propylene glycol n-butyl ether, dipropylene glycol methyl ether, propylene glycol methyl ether, propylene glycol n-propyl ether, diethylene glycol monobutyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, triethylene glycol monobutyl ether, dipropylene glycol n-propyl ether, n-butyl ether, or mixtures thereof. Preferred fusing agents include TEXANOL ester alcohols available from Eastman Chemical Company, Coasol, and Chemoxy International Ltd. Coasol and Coasol 290 Plus fusing agents available from Co., Ltd., dipropylene glycol n-butyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, n-butyl ether, or mixtures thereof. The fusing agent may be present in an amount of 0 to 3.0 wt%, 0.1 wt% to 2.0 wt%, or 0.2 wt% to 1.5 wt%, based on the total weight of the aqueous coating composition.

The aqueous coating composition of the present invention may further comprise one or more dispersants. Dispersants include non-ionic, anionic and cationic dispersants such as polyacids of suitable molecular weight, 2-amino-2-methyl-1-propanol (AMP), dimethyl amino ethanol (DMAE), potassium tripolyphosphate (KTPP) , trisodium polyphosphate (TSPP), citric acid and other carboxylic acids. The polyhydric acids used may include homopolymers and copolymers based on polycarboxylic acids (eg, molecular weight of 1,000 to 50,000 as determined by GPC), which are hydrophobically- or hydrophilically-modified, for example polyacrylic acid or polymethacrylic acid or maleic anhydride with various monomers such as styrene, acrylate or methacrylate esters, diisobutylene, and other hydrophilic or hydrophobic comonomers; salts thereof; or mixtures thereof. The dispersant may be present in an amount of 0 to 1.0 wt%, 0.1 wt% to 0.8 wt%, or 0.2 wt% to 0.6 wt%, based on the total weight of the aqueous coating composition.

The aqueous coating composition of the present invention may include one or more cryoprotectants that do not contribute to VOCs. Specific examples of the cryoprotectant may include polyethylene glycol, RHODOLINE FT-100 freeze-thaw stabilizer available from Solvay, or a mixture thereof. The cryoprotectant, if present, may be present in an amount of, for example, up to 0.5% by weight, up to 0.4%, or up to 0.1% by weight, based on the total weight of the aqueous coating composition, without weakening the antifouling properties of the coating prepared therefrom. must exist as Preferably, the aqueous coating composition is substantially free of cryoprotectants (eg, less than 0.1% or even less than 0.05%).

In addition to the elements described above, the aqueous coating composition of the present invention may further comprise any one or combination of the following additives: a buffer, a neutralizing agent, a humectant, a mildewcide, a biocide, a coating agent. anti-skinning agents, colorants, glidants, crosslinking agents, antioxidants, plasticizers, leveling agents, thixotropic agents, adhesion promoters, and grind vehicles. These additives may be present in a combined amount of 0 to 1 wt %, or 0.1 wt % to 0.8 wt %, based on the total weight of the aqueous coating composition.

The aqueous coating composition of the present invention comprises adding water, usually present in an amount of from 30% to 90% by weight, from 40% to 80% by weight, or from 50% to 70% by weight, based on the total weight of the aqueous coating composition. can be included as

The aqueous coating composition of the present invention can be prepared by mixing an aqueous polymer composition with at least one element selected from the group consisting of dispersants, fusing agents, wetting agents, thickeners, defoamers, pigments, and extenders. The components in the aqueous coating composition can be mixed in any order to provide the aqueous coating composition of the present invention. Also, any of the above-mentioned optional elements may be added to the composition during or prior to mixing to form the aqueous coating composition. The pigment and/or extender is preferably mixed with the dispersant to form a slurry of the pigment and/or extender.

The aqueous coating composition of the present invention can be applied and adhered to a variety of substrates. Examples of suitable substrates include wood, metal, plastic, foam, stone, elastic substrates, glass, wallpaper, fibers, medium-density fiberboard (MDF), particle board, gypsum board, concrete or cement substrates. The aqueous coating composition may be applied to the substrate by any necessary means including brushing, dipping, rolling and spraying. The aqueous composition is preferably applied by spraying. Standard spraying techniques and equipment for spraying, such as air-atomized spraying, air spraying, airless spraying, high volume low pressure spraying, and electrostatic spraying, such as electrostatic bell application, are manual or by an automatic method. After application of the aqueous coating composition to the substrate, the coating composition is dried or allowed to dry to form a film (ie, coating) at room temperature (20-25° C.), or at elevated temperatures, for example, 35° C. to 60° C. can do. The coating compositions may be used alone or in combination with other coatings to form multilayer coatings.

The aqueous coating composition of the present invention is useful as a coating on a variety of substrates, such as their surfaces normally exposed to the outdoors, where good beading effect and good antifouling properties are important. The aqueous coating composition has a variety of applications, such as marine and protective coatings, automotive coatings, traffic paints, exterior insulation and finishing systems (EIFS), roof mastic, wood coatings, coil coatings, plastic coatings, can coatings, construction Suitable for coatings, and civil engineering coatings. Aqueous coating compositions are particularly useful for architectural coatings.

Example

Some embodiments of the present invention will be described in the Examples below, wherein all parts and percentages are by weight unless otherwise stated.

butyl acrylate (BA), methacrylic acid (MAA), ethyl acrylate (EA), 2-ethylhexyl acrylate (2-EHA), methyl methacrylate (MMA), monoethanolamine (MEA), and TERGITOL 15-s-40 nonionic surfactants (“15-s-40”) are all available from The Dow Chemical Company.

DISPONIL FES 32 surfactant (“Fes-32”) is a fatty alcohol ether sulfate.

DISPONIL A-19 IS surfactant (“A-19”) is sodium dodecyl (linear) benzene sulfonate. Both of these surfactants are available from BASF.

ADEKA REASOAP SR-1025 Surfactant (“SR-1025”), available from Adeka, is an anionic polymerizable emulsifier (25% active).

HITENOL AR-1025 surfactant (“AR-1025”), available from Dai-Ichi Kogyo Seiyaku Co., Ltd., is a polyoxyethylene styrenated propenyl phenyl ether sulfate ammonium salt (25% active).

VISIOMER MPEG 1005 MA (“MPEG-1005MA”), available from The Evonik Company, is a polyalkylene oxide lauryl methacrylate.

Polystep P-12A surfactant (“P-12A”), available from Stepan, is polyethylene glycol monotridecyl ether phosphate (25% active).

RHODAFAC PE3016 surfactant (“PE3016”), available from Solvay, is an alkoxylated phosphate ester surfactant.

CoatOSil MP 200 Silane (“MP200”) is an epoxy functional polysiloxane oligomer having a number-average molecular weight of 350 to 1,000. Silquest A-171 Silane (“A-171”) is a vinyltrimethoxysilane. Silquest A-187 Silane (“A-187”) is gamma-glycidoxypropyltrimethoxysilane. MP200, A-171, and A-187 silanes are all available from Momentive Performance Material Inc.

Phosphoethyl methacrylate (PEM) is available from Solvay (100% active).

Shanghai Yuyou Industrial Co., Ltd. PP-7025, available from the company, is a poly[oxy(methyl-1,2-ethanediyl)], .alpha.-2-propenyl-, omega, -hydroxy, -phosphate ammonium salt (25% active) . SIPOMER PAM-200 (“PAM-200”), available from Solvay, is a methylacrylate alkoxylated ether phosphate containing ˜5 PO units (100% active). SIPOMER COPS-3 (“COPS-3”), available from Solvay, is an allyl alkoxylated ether phosphate ammonium salt (40% active). UCAN-5, UCAN-6, UCAN-7 and UCAN-9 allyl alkoxylated ether phosphate ammonium salts are all available from Shanghai Honesty Fine Chemical Co., Ltd. The structures of these surfactants are given below,

The following standard analytical equipment and methods were used in the Examples.

Freeze/Thaw (F/T) Stability Evaluation

The container was filled with 75% volume of the test coating composition. The container was sealed and placed in a freezer at -6°C for 16 hours, then removed from the freezer and thawed at ambient conditions (about 25°C) for 8 hours. This step completed one F/T cycle. The F/T cycle continued until the sample solidified or up to 3 cycles. After each cycle, the cycle number was recorded if clots or gels were observed. After completion of 3 cycles, the samples were manually shaken and visually observed for appearance. If, after the freeze-thaw test, the sample does not coagulate, or if no grit detached from the sample is visible, the sample is graded "Pass", indicating good freeze-thaw stability. Otherwise, if the sample coagulates or has segregated grit, the sample is graded "Fail", indicating poor freeze-thaw stability.

brush clogging test

A test sample was prepared by mixing 100 g of the test coating composition with 20 g of water. The resulting mixture was poured into a can. Next, a wooden brush was placed in the can and placed in an oven at 40° C. for 2 hours. The heated brush was removed, brushed on the board, and then placed back in an oven-stored can. One cycle of the above steps is completed. At each cycle, if brush clogging was observed, the cycle number was recorded. After 5 cycles, the brushes were lightly washed by hand with water. If the brush is not clogged or hardened, and there is no deposit observed in the brush, the sample passes the brush clogging test, which indicates good anti-clogging performance; Otherwise, the sample fails the brush clogging test, indicating poor clog-preventing performance.

decontamination test

The decontamination ability was tested using the GB/T 9780-2013 method. The test sample is thrown onto a black vinyl scrub chart using a drawdown bar to form a wet film (thickness: 120 μm). Prior to application of contaminants, the membranes were cured at room temperature for 7 days. The test area consists of a chart cross-section of 25 mm wide and 100 mm long. Within the test area, six types of contaminants (vinegar, black tea, ink, water black, alcohol black, and petrolatum black) were applied to the membrane. Liquid contamination was applied against the gauze to prevent contamination from overflowing from the test area. After the soil was held on the panel for 2 hours, the excess soil was wiped off with a dry tissue. Thereafter, the test panel was placed on a scrubbing tester under a weight of 1.5 kg, and a scrub cycle of 37 rubs per minute was performed. After the test panel was rubbed for 200 cycles, it was removed from the tester, rinsed under running water, and hung to dry. The cleaned contaminated area was then evaluated by measuring the reflectance (X) using the following equation:

Here, Y ₁ is the reflectance after the decontamination test, and Y ₀ is the reflectance before the decontamination test. Y ₁ and Y ₀ were tested by a BYK Spectro-Guide instrument.

Based on the obtained reflectance value X, the decontamination score Ri for each contaminant can be obtained from the table below on a scale of 1 to 10.

The total decontamination score (R') was then calculated according to the following formula,

where Ri is the decontamination score for different stains, and n is 6. In China, the premium standard for decontamination is at least 60 points according to the GB method. Otherwise, a total decontamination score of less than 60 points is not acceptable. The higher the total decontamination score, the better the antifouling properties.

VOC measurement

VOC measurements were performed on an Agilent 7890A gas chromatography (GC), 5975C mass spectrometer (MS) with 3-axis detector. An aliquot of 2 g (accurately recorded) of the test coating composition was weighed into a 20 mL centrifuge vial, followed by a 500 ppm internal standard (2-(2-ethoxyethoxy)-ethanol) and a VOC marker (hexanedioic acid ( hexanedioic acid), diethyl ester) was added. The resulting sample was first shaken in a vortex mixer for 1 minute, then left for 5 minutes, then shaken for an additional 1 minute, and finally centrifuged at 4,000 rpm for 20 minutes. The supernatant of the sample was taken and filtered through a 0.45 μm syringe filter. The resulting filtrate was then injected into the GC-MS system with an injection volume of 1 μL. GC-MS conditions are as follows,

GC oven program: initial 45°C hold for 4 minutes, then hold for 10 minutes to 230°C at a rate of 8°C/min; flow rate: 1 mL/min; Average speed: 36.4 cm/sec;

GC inlet temperature: 230°C, split ratio: 10:1;

GC column: DB-5MS (J&W, part number: 122-5533): 30 m length x 250 μm diameter x 1.0 μm film thickness;

Mass Spectrometry Detector (MSD) Parameters (Scan Mode): MS Source Temperature: 230°C, MS Quad Temperature: 150°C, Acquire Mode: Scan, Mass 29-350 Da.

The content of VOC in the sample was determined based on the guidelines described in GB 18582-2008 method. The response factor of various VOCs to the internal standard was considered as '1'.

Comparative (Comp) Example (Ex) 1 Aqueous Polymer Composition

Monomer emulsion (ME) was prepared by mixing 450 g of deionized water, 60 g of A-19, 60 g of PP-7025, 712.58 g of MMA, 109.42 g of 2-EHA, 721.21 g of EA, and 23.76 g of MAA. was manufactured by

To a 5-liter, four-neck round bottom flask equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 700 g of deionized water was added and heated to 88° C. with stirring under a nitrogen atmosphere. Then 5.0 g Fes-32 and 59.6 g ME, followed by 4.68 g sodium persulfate rapidly dissolved in 28.08 g deionized water were added to the flask. The remaining ME was added to the flask while co-feeding 1.56 g sodium persulfate dissolved in 100 g deionized water within 120 minutes. When the ME feed was complete, the reaction was held at 88° C. for 40 minutes. Then, NaOH solution was added to adjust the pH to 8.0-8.5. Finally, 8.20 g of CoatOSil MP200 silane oligomer was added slowly afterwards.

Comparative Example 2 Aqueous Polymer Composition

Monomer emulsion (ME) was prepared by mixing 450 g of deionized water, 60 g of P-12A, 697.17 g of MMA, 109.42 g of 2-EHA, 721.21 g of EA, 22.29 g of MPEG-1005MA and 16.97 g of MAA. was manufactured.

To a 5-liter, four-neck round bottom flask equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 700 g of deionized water was added and heated to 88° C. with stirring under a nitrogen atmosphere. Then 5.0 g Fes-32 and 59.6 g ME, followed by 4.68 g sodium persulfate rapidly dissolved in 28.08 g deionized water were added to the flask. The remaining ME was added to the flask while co-feeding 1.56 g sodium persulfate dissolved in 100 g deionized water within 120 minutes. When the ME feed was complete, the reaction was held at 88° C. for 40 minutes. Then, NaOH solution was added to adjust the pH to 8.0-8.5. Finally, 8.20 g of CoatOSil MP200 silane oligomer was added slowly afterwards.

Example 1 Aqueous Polymer Composition

Monomer emulsion (ME) contains 450 g of deionized (DI) water, 60 g of P-12A, 60 g of PP-7025, 697.17 g of MMA, 109.42 g of 2-EHA, 721.21 g of EA, 22.29 g of It was prepared by mixing MPEG-1005MA and 16.97 g of MAA.

To a 5-liter, four-neck round bottom flask equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 700 g of deionized water was added and heated to 88° C. with stirring under a nitrogen atmosphere. Then 5.00 g Fes-32 and 59.6 g ME, followed by 4.68 g sodium persulfate rapidly dissolved in 28.08 g deionized water were added to the flask. The remaining ME was added to the flask while co-feeding 1.56 g sodium persulfate dissolved in 100 g deionized water within 120 minutes. When the ME feed was complete, the reaction was held at 88° C. for 40 minutes. Then, NaOH solution was added to adjust the pH to 8.0-8.5. Finally, 8.20 g of CoatOSil MP200 silane oligomer was added slowly afterwards.

Comparative Example 3 Aqueous Polymer Composition

A monomer emulsion (ME) was prepared by mixing 450 g of deionized water, 100 g of PE3016, 697.17 g of MMA, 109.42 g of 2-EHA, 721.21 g of EA, 22.29 g of MPEG-1005MA and 16.97 g of MAA. .

To a 5-liter, four-neck round bottom flask equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 700 g of deionized water was added and heated to 88° C. with stirring under a nitrogen atmosphere. Then 5.0 g Fes-32 and 59.6 g ME, followed by 4.68 g sodium persulfate rapidly dissolved in 28.08 g deionized water were added to the flask. The remaining ME was added to the flask while co-feeding 1.56 g sodium persulfate dissolved in 100 g deionized water within 120 minutes. When the ME feed was complete, the reaction was held at 88° C. for 40 minutes. Then, NaOH solution was added to adjust the pH to 8.0-8.5. Finally, 8.20 g of CoatOSil MP200 silane oligomer was added slowly afterwards.

Comparative Example 4 Aqueous Polymer Composition

Monomer emulsion (ME) comprises 450 g of deionized water, 60 g of P-12A, 60 g of SR-1025, 697.17 g of MMA, 109.42 g of 2-EHA, 721.21 g of EA, 22.29 g of MPEG-1005MA and It was prepared by mixing 16.97 g of MAA.

To a 5-liter, four-neck round bottom flask equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 700 g of deionized water was added and heated to 88° C. with stirring under a nitrogen atmosphere. Then 5.0 g Fes-32 and 59.6 g ME, followed by 4.68 g sodium persulfate rapidly dissolved in 28.08 g deionized water were added to the flask. The remaining ME was added to the flask while co-feeding 1.56 g sodium persulfate dissolved in 100 g deionized water within 120 minutes. When the ME feed was complete, the reaction was held at 88° C. for 40 minutes. Then, NaOH solution was added to adjust the pH to 8.0-8.5. Finally, 8.20 g of CoatOSil MP200 silane oligomer was added slowly afterwards.

Comparative Example 5 Aqueous Polymer Composition

Monomer emulsion (ME) comprises 450 g of deionized water, 60 g of P-12A, 60 g of AR-1025, 697.17 g of MMA, 109.42 g of 2-EHA, 721.21 g of EA, 22.29 g of MPEG-1005MA and It was prepared by mixing 16.97 g of MAA.

To a 5-liter, four-neck round bottom flask equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 700 g of deionized water was added and heated to 88° C. with stirring under a nitrogen atmosphere. Then 5.0 g Fes-32 and 59.6 g ME, followed by 4.68 g sodium persulfate rapidly dissolved in 28.08 g deionized water were added to the flask. The remaining ME was added to the flask while co-feeding 1.56 g sodium persulfate dissolved in 100 g deionized water within 120 minutes. When the ME feed was complete, the reaction was held at 88° C. for 40 minutes. Then, NaOH solution was added to adjust the pH to 8.0-8.5. Finally, 8.20 g of CoatOSil MP200 silane oligomer was added slowly afterwards.

Example 2 Aqueous Polymer Composition

The aqueous polymer composition of Example 2 was prepared in which the monomer emulsion used in Example 2 was 450 g of deionized water, 60 g of P-12A, 60 g of UCAN-5, 697.17 g of MMA, 109.42 g of 2-EHA, It was prepared in the same manner as in Example 1, except that it was prepared by mixing 721.21 g of EA, 22.29 g of MPEG-1005MA and 16.97 g of MAA.

Example 3 Aqueous Polymer Composition

The aqueous polymer composition of Example 3 was prepared in which the monomer emulsion used in Example 3 was 450 g of deionized water, 60 g of P-12A, 60 g of UCAN-7, 697.17 g of MMA, 109.42 g of 2-EHA, It was prepared in the same manner as in Example 1, except that it was prepared by mixing 721.21 g of EA, 22.29 g of MPEG-1005MA and 16.97 g of MAA.

Example 4 Aqueous Polymer Composition

The aqueous polymer composition of Example 4 was prepared in which the monomer emulsion used in Example 4 was 450 g of deionized water, 60 g of P-12A, 6.67 g of PP-7025, 697.17 g of MMA, 109.42 g of 2-EHA, It was prepared in the same manner as in Example 1, except that it was prepared by mixing 721.21 g of EA, 22.29 g of MPEG-1005MA and 16.97 g of MAA.

Example 5 Aqueous Polymer Composition

The aqueous polymer composition of Example 5 was prepared wherein the monomer emulsion used in Example 5 was 450 g of deionized water, 60 g of P-12A, 25.71 g of PP-7025, 697.17 g of MMA, 109.42 g of 2-EHA, It was prepared in the same manner as in Example 1, except that it was prepared by mixing 721.21 g of EA, 22.29 g of MPEG-1005MA and 16.97 g of MAA.

Example 6 Aqueous Polymer Composition

The aqueous polymer composition of Example 6 was prepared in which the monomer emulsion used in Example 6 was 450 g of deionized water, 60 g of P-12A, 140 g of PP-7025, 697.17 g of MMA, 109.42 g of 2-EHA, It was prepared in the same manner as in Example 1, except that it was prepared by mixing 721.21 g of EA, 22.29 g of MPEG-1005MA and 16.97 g of MAA.

Example 7 Aqueous Polymer Composition

The aqueous polymer composition of Example 7 was prepared in which the monomer emulsion used in Example 7 was 450 g deionized water, 60 g P-12A, 540 g PP-7025, 697.17 g MMA, 109.42 g 2-EHA, It was prepared in the same manner as in Example 1, except that it was prepared by mixing 721.21 g of EA, 22.29 g of MPEG-1005MA and 16.97 g of MAA.

Example 8 Aqueous Polymer Composition

Monomer emulsion (ME) comprises 450 g of deionized water, 60 g of P-12A, 60 g of PP-7025, 697.17 g of MMA, 109.42 g of 2-EHA, 721.21 g of EA, 22.29 g of MPEG-1005MA and It was prepared by mixing 16.97 g of MAA.

To a 5-liter, four-neck round bottom flask equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 700 g of deionized water was added and heated to 88° C. with stirring under a nitrogen atmosphere. Then 5.0 g Fes-32 and 59.6 g ME, followed by 4.68 g sodium persulfate rapidly dissolved in 28.08 g deionized water were added to the flask. The remaining ME was added to the flask while co-feeding 1.56 g sodium persulfate dissolved in 100 g deionized water within 120 minutes. When the ME feed was complete, the reaction was held at 88° C. for 40 minutes. Then, NaOH solution was added to adjust the pH to 8.0-8.5. Finally, 8.20 g of Silquest A-187 silane was added slowly afterwards.

Example 9 Aqueous Polymer Composition

Monomer emulsion (ME) comprises 450 g of deionized water, 60 g of P-12A, 60 g of PP-7025, 697.17 g of MMA, 109.42 g of 2-EHA, 721.21 g of EA, 22.29 g of MPEG-1005MA and It was prepared by mixing 16.97 g of MAA.

To a 5-liter, four-neck round bottom flask equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 700 g of deionized water was added and heated to 88° C. with stirring under a nitrogen atmosphere. Then 5.0 g Fes-32 and 59.6 g ME, followed by 4.68 g sodium persulfate rapidly dissolved in 28.08 g deionized water were added to the flask. The remaining ME was added to the flask while co-feeding 1.56 g sodium persulfate dissolved in 100 g deionized water within 120 minutes. When the ME feed was complete, the reaction was held at 88° C. for 40 minutes. Then, NaOH solution was added to adjust the pH to 8.0-8.5. Finally, 8.20 g of Silquest A-171 silane was added slowly afterwards.

Comparative Example 6 Aqueous Polymer Composition

The aqueous polymer composition of Comparative Example 6 was prepared in which the monomers used in Comparative Example 6 were 450 g of deionized water, 60 g of P-12A, 60 g of UCAN-6, 697.17 g of MMA, 109.42 g of 2-EHA, 721.21 It was prepared in the same manner as in Example 1, except that it was prepared by mixing g of EA, 22.29 g of MPEG-1005MA, and 16.97 g of MAA.

Comparative Example 7 Aqueous Polymer Composition

The aqueous polymer composition of Comparative Example 7, wherein the monomer emulsion used in Comparative Example 7 was 450 g of deionized water, 60 g of P-12A, 37.5 g of COPS-3, 697.17 g of MMA, 109.42 g of 2-EHA, It was prepared by the same procedure as in Example 1, except that it was prepared by mixing 721.21 g of EA, 22.29 g of MPEG-1005MA, and 16.97 g of MAA.

Comparative Example 8 Aqueous Polymer Composition

The aqueous polymer composition of Comparative Example 8 was prepared in which the monomer emulsion used in Comparative Example 8 was 450 g of deionized water, 60 g of P-12A, 60 g of UCAN-9, 697.17 g of MMA, 109.42 g of 2-EHA, It was prepared in the same manner as in Example 1, except that it was prepared by mixing 721.21 g of EA, 22.29 g of MPEG-1005MA and 16.97 g of MAA.

Comparative Example 9 Aqueous Polymer Composition

The aqueous polymer composition of Comparative Example 9 was prepared in which the monomer emulsion used in Comparative Example 9 was 450 g of deionized water, 60 g of P-12A, 15 g of PEM, 697.17 g of MMA, 109.42 g of 2-EHA, 721.21 g EA, 22.29 g of MPEG-1005MA, and 16.97 g of MAA were prepared by the same procedure as in Example 1, except that it was prepared by mixing.

Comparative Example 10 Aqueous Polymer Composition

The aqueous polymer composition of Comparative Example 10 was prepared in which the monomer emulsion used in Comparative Example 10 was 450 g of deionized water, 60 g of P-12A, 15 g of PAM-200, 697.17 g of MMA, 109.42 g of 2-EHA, It was prepared in the same manner as in Example 1, except that it was prepared by mixing 721.21 g of EA, 22.29 g of MPEG-1005MA and 16.97 g of MAA.

Comparative Example 11 Aqueous Polymer Composition

Monomer emulsion (ME) comprises 450 g of deionized water, 60 g of P-12A, 60 g of PP-7025, 697.17 g of MMA, 109.42 g of 2-EHA, 721.21 g of EA, 22.29 g of MPEG-1005MA and It was prepared by mixing 16.97 g of MAA.

To a 5-liter, four-neck round bottom flask equipped with a paddle stirrer, thermometer, nitrogen inlet and reflux condenser, 700 g of deionized water was added and heated to 88° C. with stirring under a nitrogen atmosphere. Then 5.0 g Fes-32 and 59.6 g ME, followed by 4.68 g sodium persulfate rapidly dissolved in 28.08 g deionized water were added to the flask. The remaining ME was added to the flask while co-feeding 1.56 g sodium persulfate dissolved in 100 g deionized water within 120 minutes. When the ME feed was complete, the reaction was held at 88° C. for 40 minutes. Then, NaOH solution was added to adjust the pH to 8.0-8.5.

All aqueous polymer compositions obtained above have a measured particle size of about 130 nm and a solids content of about 47%.

coating composition

The coating composition was prepared based on the recipe shown in Table 1. The prepared aqueous polymer compositions (Examples 1 to 9 and Comparative Examples 1 to 11) were used as binders for preparing each coating composition by the method shown in Table 2. The ingredients for grinding were mixed using a high speed Cowles disperser. Then, the ingredients for letdown were added and mixed by means of a conventional agitator. The obtained coating composition was tested according to the test method described above, and the results are presented in Table 2. All coating compositions had a VOC of less than 5 g/L, as measured according to the GB18582-2008 method.

As shown in Table 2, a polymer obtained from a reactive allyl alkoxylated phosphorus-containing monomer having 3-5 PO units was combined with a P-12A phosphorus-containing surfactant and a functional silane (Example 1-9 binder). The binder comprising gave the coating good antifouling properties (decontamination score of 60-65), while surprisingly maintaining good F/T stability and anti-clogging properties for the zero VOC coating composition.

Conversely, when combining the A-19 surfactant with a polymer having structural units of PP-7025 reactive phosphate monomer (Comparative Example 1 binder), the decontamination score of the resulting coating was very low (~46). P-12A surfactant (comparative example 2 binder), PE3016 phosphorus-containing surfactant (comparative example 3 binder), or other reactive alkoxylate sulfate surfactant (SR-1025 or AR-1025) (comparative example 4 and 5 binder) ), the resulting binder gave the coating poor stain removal performance. Binders obtained from reactive allyl alkoxylate phosphate monomers with ethylene oxide units but no propylene oxide units (Comparative Examples 6 and 7 binders) provided the coating with poor antifouling properties and disproportionate F/T stability and anti-clogging properties. A binder obtained from an allyl alkoxylate phosphate monomer having 8 PO units (Comparative Example 8 binder) failed the F/T stability test. The use of reactive methacrylate phosphate monomers (Comparative Examples 9 and 10 binders) also results in poor antifouling properties, F/T stability and anti-clogging performance properties of the coating. The binder containing no functional silane (Comparative Example 11 binder) provided poor antifouling properties, as indicated by a stain removal score of <60 in the zero VOC coating composition.

Claims (9)

An aqueous polymer composition comprising:
(i) from 0.1% to 10% by weight, based on the weight of the polymer, of structural units of an allyl alkoxylated phosphorus-containing monomer having the structure of formula (I);

(I);
(wherein m is 2 to 5, n is 0 to 10, 1 is 1 or 2, Y is -OH or -O ^- M ⁺ , wherein M is a metal ion or an ammonium ion);
(ii) a functional silane selected from an epoxy functional polysiloxane oligomer, an epoxy functional silane compound, an ethylenically unsaturated compound having at least one alkoxysilane functional group, or mixtures thereof; and
(iii) a phosphorus-containing surfactant having the structure of formula (V);

(V),
(wherein R is C ₈ -C ₃₀ alkyl, AO is an alkoxylated group, b is 1-2, a is 1-30, and N ⁺ is a metal ion or ammonium ion). ◈Claim 2 was abandoned when paying the registration fee.◈ According to claim 1, wherein in the formula (I), m is 3 to 5, n is 0 to 5, Y is -O ^- M ⁺ , wherein M is a metal ion or an ammonium ion. The aqueous polymer composition of claim 1 , wherein the polymer comprises from 0.5% to 3% by weight of structural units of an allyl alkoxylated phosphorus-containing monomer, based on the weight of the polymer. The method of claim 1, wherein the epoxy-functional polysiloxane oligomer has the following structure (III),

(III),
wherein x is 0 to 14 and R ₃ is —CH ₂ CH ₂ CH ₂ —. The method of claim 1, wherein the functional silane is 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, 3-glycidyloxypropyl methyldiethoxysilane, 3-glycidyloxypropyl An aqueous polymer composition selected from the group consisting of cidyloxypropyl methyldimethoxysilane, vinyltrialkoxysilane, alkylvinyldialkoxysilane, and (meth)acryloxyalkyltrialkoxysilane. The aqueous polymer composition of claim 1 , wherein the functional silane is present in an amount of 0.1% to 3% by weight based on the weight of the polymer. ◈Claim 7 was abandoned at the time of payment of the registration fee.◈ The aqueous polymer composition of claim 1 , wherein the polymer further comprises 0.1% to 5% by weight of structural units of an ethylenically unsaturated alkoxylated (meth)acrylate monomer, based on the weight of the polymer. ◈Claim 8 was abandoned when paying the registration fee.◈ The aqueous polymer composition of claim 1 comprising 0.1% to 5% by weight of a phosphorus-containing surfactant, based on the weight of the polymer. ◈Claim 9 was abandoned at the time of payment of the registration fee.◈ having a VOC content of 5 g/L or less, wherein the aqueous polymer composition of any one of claims 1 to 8, and at least one selected from the group consisting of dispersants, fusing agents, wetting agents, thickeners, defoamers, pigments, and extenders An aqueous coating composition comprising urea.